CA2119411A1 - (co) polymerization process in aqueous emulsion of fluorinated olefinic monomers - Google Patents
(co) polymerization process in aqueous emulsion of fluorinated olefinic monomersInfo
- Publication number
- CA2119411A1 CA2119411A1 CA002119411A CA2119411A CA2119411A1 CA 2119411 A1 CA2119411 A1 CA 2119411A1 CA 002119411 A CA002119411 A CA 002119411A CA 2119411 A CA2119411 A CA 2119411A CA 2119411 A1 CA2119411 A1 CA 2119411A1
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- Canada
- Prior art keywords
- process according
- chain transfer
- transfer agent
- carbon atoms
- hydrogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Abstract
(CO)POLYMERIZATION PROCESS IN AQUEOUS EMULSION OF
FLUORINATED OLEFINIC MONOMERS.
ABSTRACT
Radical (co)polymerization process of fluorinated olefinic monomers, optionally in association with one or more non-fluorinated olefins, in which the monomers are (co)polymerized in aqueous emulsion, in the presence of a hydrogenated chain transfer agent selected from hydrogen, aliphatic hydrocarbons and fluorohydrocarbons C1-C20 and of a branched chain aliphatic alcohol C3-C12 characterized by a ratio between the number of hydroxyl groups and the number of methyl groups lower than or equal to 0.5.
FLUORINATED OLEFINIC MONOMERS.
ABSTRACT
Radical (co)polymerization process of fluorinated olefinic monomers, optionally in association with one or more non-fluorinated olefins, in which the monomers are (co)polymerized in aqueous emulsion, in the presence of a hydrogenated chain transfer agent selected from hydrogen, aliphatic hydrocarbons and fluorohydrocarbons C1-C20 and of a branched chain aliphatic alcohol C3-C12 characterized by a ratio between the number of hydroxyl groups and the number of methyl groups lower than or equal to 0.5.
Description
2 21~9~
The present invention relates to a polymerization process in aqueous emulsion of fluorinated olefinic monomers, in which hydrogenated chain transfer agents are used, in association with branched chain aliphatic alcohols.
It is known to utilize hydrogen or hydrocarbons or fluorohydrocarbons having low molecular weight as chain transfer agents in polymerization reactions in aqueous emulsion of fluorinated olefinic monomers, optionally in association with fully hydrogenated olefins. Such transfer agents show the advantage of giving non-polar end groups, more stable than the end groups obtainable with other chain transfer agents (such as methanol).
For instance, in US Patent 3,635,926 a copolymerization process of tetrafluoroethylene with perfluoroalkylvinyl~
ethers in aqueous emulsion is described, wherein hydrogen, methane or ethane are used as chain transfer agents. To obtain a sufficient chain transfer effect, it is necessary to employ such transfer agents, which are all above the critical temperature in the usual polymerization conditions, with high partial pressures. Consequently, by acting at the same operating pressure, it is obtained a reduction in the monomer partial pressure, and therefore an increase of the low molecular weight fractions in the final product, with unavoidable worsening of the mechanical properties. To avoid 3 21~3~11 that, the operating pressure could be increased, but this would cause evident plant drawbacks, particularly when tetrafluoroethylene is used, for which it is recommended for safety reasons operating at a pressure as low as possible.
The Applicant has now surprisingly found that it is possible to considerably increase the efficiency of the hydrogenated chain transfer agents by adding to the reaction mixture a branched chain aliphatic alcohol.
It is, therefore, an object of the present invention a radical (co)polymerization process of one or more fluorinated olefinic monomers, optionally in association with one or more non-fluorinated olefins, wherein said monomers are (co)polymerized in aqueous emulsion, in the presence of a hydrogenated chain transfer agent selected from hydrogen, aliphatic hydrocarbons and fluorohydrocarbons having from 1 to 20, preferably from 1 to 8, carbon atoms, and of a branched chain aliphatic alcohol, having from 3 to 14, preferably from 3 to 8, carbon atoms and characterized by a ratio among the number of hydroxyl groups and the number of methyl groups lower than or equal to 0.5.
The presence of the branched chain alcohol, by increasing the effectiveness of the hydrogenated chain transfer agent, allows to employ the latter with lower partial pressures and therefore it reduces the formation of low molecular weight fractions. Moreover, the addition of the branched chain alcohol allows an effective control of the molecular weight without impairing the reaction rate and therefore the process productivity.
The present invention relates to a polymerization process in aqueous emulsion of fluorinated olefinic monomers, in which hydrogenated chain transfer agents are used, in association with branched chain aliphatic alcohols.
It is known to utilize hydrogen or hydrocarbons or fluorohydrocarbons having low molecular weight as chain transfer agents in polymerization reactions in aqueous emulsion of fluorinated olefinic monomers, optionally in association with fully hydrogenated olefins. Such transfer agents show the advantage of giving non-polar end groups, more stable than the end groups obtainable with other chain transfer agents (such as methanol).
For instance, in US Patent 3,635,926 a copolymerization process of tetrafluoroethylene with perfluoroalkylvinyl~
ethers in aqueous emulsion is described, wherein hydrogen, methane or ethane are used as chain transfer agents. To obtain a sufficient chain transfer effect, it is necessary to employ such transfer agents, which are all above the critical temperature in the usual polymerization conditions, with high partial pressures. Consequently, by acting at the same operating pressure, it is obtained a reduction in the monomer partial pressure, and therefore an increase of the low molecular weight fractions in the final product, with unavoidable worsening of the mechanical properties. To avoid 3 21~3~11 that, the operating pressure could be increased, but this would cause evident plant drawbacks, particularly when tetrafluoroethylene is used, for which it is recommended for safety reasons operating at a pressure as low as possible.
The Applicant has now surprisingly found that it is possible to considerably increase the efficiency of the hydrogenated chain transfer agents by adding to the reaction mixture a branched chain aliphatic alcohol.
It is, therefore, an object of the present invention a radical (co)polymerization process of one or more fluorinated olefinic monomers, optionally in association with one or more non-fluorinated olefins, wherein said monomers are (co)polymerized in aqueous emulsion, in the presence of a hydrogenated chain transfer agent selected from hydrogen, aliphatic hydrocarbons and fluorohydrocarbons having from 1 to 20, preferably from 1 to 8, carbon atoms, and of a branched chain aliphatic alcohol, having from 3 to 14, preferably from 3 to 8, carbon atoms and characterized by a ratio among the number of hydroxyl groups and the number of methyl groups lower than or equal to 0.5.
The presence of the branched chain alcohol, by increasing the effectiveness of the hydrogenated chain transfer agent, allows to employ the latter with lower partial pressures and therefore it reduces the formation of low molecular weight fractions. Moreover, the addition of the branched chain alcohol allows an effective control of the molecular weight without impairing the reaction rate and therefore the process productivity.
4 21~9~1 Moreover, the experimentation performed by the Applicant demonstrates that the branched chain alcohol by itself exerts an irrelevant activity as chain transfer agent. Therefore, the alcohol acts only as activator with respect to the actual chain transfer agent. This fact is very important for the stability of the final product, since a transfer activity of the alcohol would lead to an undesired introduction of polar moieties as end groups.
Moreover, the addition of the branched chain alcohol makes effective as chain transfer agents also those hydrocarbons which have low activity by themselves. For ;~
instance, with the process object of the present invention it is possible to employ as chain transfer agents n-pentane and other hydrocarbons liquid at room temperature, which can be more easily handled and dosed if compared with gaseous hydrocarbons such as methane and ethane.
Examples of hydrogenated chain transfer agents employable in the process object of the present invention are: methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane, l,l-difluoroethane, or mixtures thereof. -~
~ xamples of branched chain aliphatic alcohols employable in the process object of the present invention are: isopropanol, terbutanol, pinacol, 2,4-dimethyl-3-pentanol, 2,4,4-trimethyl-1,3-pentandiol, or mixtures thereof.
The amount of hydrogenated chain transfer agent and of ' ' 21~ 9 L~ 1 1 aliphatic alcohol to be used can vary within a very wide range and depends on various factors, such as the polymerization conditions (in particular temperature, presence of co-solvents, etc.), the monomer nature, besides, of course, on the structure of the chain transfer agent and of the alcohol. According to the characteristics of the final product to be obtained, the skilled person will be able to choose case by case the most suitable concentrations of chain transfer agent and of alcohol. For indicative purposes the weight ratio between alcohol and transfer agent can vary from 0.005 to 500, preferably from 0.05 to 50.
The (co)polymerization is carried out in aqueous emulsion according to methods well known in the art (see for instance US patents 3,635,926 and 4,426,501). Preferably, the process is carried out in aqueous emulsion in the presence of an emulsion or microemulsion of perfluoropoly~
oxyalkylenes, according to what described in US Patents 4,789,717 and 4,864,006. ~;~
As known in the art, the (co)polymerization reaction occurs in the preæence of suitable initiators, such as inorganic (for instance, ammonium or alkali metal per-sulphates) or organic (for instance, disuccinylperoxide, terbutyl-hydroperoxide, diterbutyl-peroxide) peroxides, or also azo-compounds (see US 2,515,628 and 2,520,338). It is also possible to employ organic or inorganic redox systems, such as ammonium persulphate/sodium sulphite, hydrogen peroxide/aminoiminomethansulphinic acid. The amount of ",.~" ,,,., . ~ . ~, ",,," ,,,,,, 1 ,.
2~9~
radical initiator is that commonly employed for the (co)polymerization of fluorinated olefinic monomers, and it is generally comprised between 0.003% and 2% by weight with respect to the total amount of (co)polymerized monomers.
As known, the emulsion technique requires also the presence of surfactants. Among the various kinds of surfactants employable in the process object of the present invention, we would like to cite in particular the products of formula:
R~-X- M~
where Rf is a (per)fluoroalkyl chain Cs-C16 or a (per)fluoro-polyoxyalkylene chain, X~ is -COO~ or -S03-, M~ is selected from H~, NH~, alkali metal ion. The most commonly used are:
ammonium perfluoro-octanoate, (per)fluoropolyoxyalkylenes end-capped with one or more carboxylic groups, etc.
The reaction temperature can vary within wide ranges, generally comprised between 10 and 150C, preferably be~ween 50 and 80C, while the pressure is generally comprised between 10 and 100 bar, preferably between 15 and 40 bar.
The process object of the present invention can be employed with all kinds of fluorinated olefinic monomers, optionally containing hydrogen and/or chlorine and/or bromine and/or iodine and/or oxygen, provided that they are able to give rise to (co)polymers for reaction with radical initiators in aqueous emulsion. Among them we cite:
perfluoroolefins C2-C8, such as tetrafluoroethylene (TFE), hexafluoropropene (HFP), hexafluoroisobutene; hydrogenated 21~9411 fluoroolefins C2-C~, such as vinyl fluoride (VF), vinylidene fluoride (VDF) and trifluoroethylene; chloro- and/or bromo~
and/or iodo-fluoroolefins C2_CBI such as chlorotrifluoro-ethylene (CTFE) and bromotrifluoroethylene; perfluorovinyl-ethers CF2=CFOX, where X is a perfluoroalkyl Cl-C6, for instance trifluoromethyl or pentafluoropropyl, or a perfluoro-oxyalkyl Cl-Cg having one or more ethereal groups, for example perfluoro-2-propoxy-propyl; perfluorodioxols.
The fluoroolefins can be also copolymerized with non-fluorinated olefins C2-C8, such as ethylene, propylene, iso-butylene.
Among the copolymers to which the process object of the present invention can be applied are comprised in particular~
(a) "modified'l polytetrafluoroethylene, containing small amounts, generally comprised between 0.1 to 3% by mols, preferably lower than 0.5% by mols, of one or more comonomers such as, for example: perfluoropropene, perfluoroalkylvinylethers, vinylidene fluoride, hexafluoroisobutene, chlorotrifluoroethylenei (b) TFE thermoplastic polymers containing from 0.5 to 8% by mols of at least a perfluoroalkylvinylether, where the alkyl has from 1 to 6 carbon atoms, such as, for instance, TFE/perfluoropropylvinylether and TFE/
perfluoromethylvinylether copolymers;
(c) TFE thermoplastic polymers containing fr~m 2 to 20~ by mols of a perfluoroolefin C3_C~, such as, for example, FEP (TFE/HFP copolymer), to which other comonomers 21~9~11 having vinylether structure can be added in small amounts (lower than 5% by mols) (see for instance US
patent 4,675,380);
(d) TFE or CTFE copolymers with ethylene, propylene or isobutylene, optionally containing a third fluorinated comonomer in amounts comprised between 0.1 and 10% by mols (see for instance US patents 3,624,250 and 4,513,129);
(e) TFE elastomeric copolymers with a perfluoro(oxy)alkyl-vinylether, optionally containing propylene or ethylene, besides lower amounts of a ~'cure-site"
monomer (see for instance US patents 3,467,635 and 4,694,045);
(f) polymers having dielectric characteristics, comprising 60-79% by mols of VDF, 18-22% by mols of trifluoro-ethylene and 3-22% by mols of CTFE (see US patent 5,087,679).
(g) VDF elastomeric polymers, such as VDF/HFP copolymers and VDF/HFP/TFE terpolymers (see, for instance, GB
Patent 888,765 and Kirk-Othmer, "Encyclopedia of Chemical Technology", Vol. 8, pag. 500-515 - 1979);
such polymers can also contain: hydrogenated olefins, such as ethylene and propylene (as described for instance in EP-518,073); perfluoroalkylvinylethersi bromine "cure-site" comonomers and/or terminal iodine atoms, according to what described, for instance, in US-4,243,770, US-4,973,633 and EP-407,937.
(h) polyvinylidenfluoride or "modified~ polyvinyliden-~' ',~' 2 1 ~
fluoride containing little amounts, generally comprisedbetween 0.1 and 10~ by mols, of one or more fluorinated comonomers, such as hexafluoropropene, tetrafluoro-ethylene, trifluoroethylene.
The polymers of the above indicated classes, and in particular the TFE polymers, can be modified with : ~ .
perfluorinated dioxols, according to what described for instance in US-3,865,845, US-3,978,030, EP-73,087, EP~
76,581, EP-80,187.
Some examples are reported hereinbelow, for merely illustrative and not limitative purposes of the invention itself.
Preparation of the perfluoropolyoxyalkylene microemulsion In a glass flask equipped with a stirrer, 29.3 g of a compound of formula:
CF30 - ( CF2 - CF ( CF3 ) O ) n ( CF20 ) ,- CF2COOH
having n/m=10 and average molecular weight of 590, were mixed with 16.3 g of NH~OH at 30~ by volume. 32.6 g of demineralized water and 17.6 g of Galden~R~ D02 of formula:
CF30- (CF2-CF (CF3) O) n (CF20) ,-CF3 having n/m=20 and average molecular weight of 450, were then added. At a temperature of from 60 to 90C the mixture was ;
in the form of a microemulsion and appeared as a limpid, thermodynamically stable solution.
~A~PLE 1 An AISI 316 chromium steel 5 1 autoclave, equipped with a stirrer working at 650 rpm, was evacuated and there were introduced in sequence: 3 1 of demineralized water; 32.33 g .
'.~.
~'' lo 21~
per H2O liter of perfluoropropylvinylether (PPVE); the microemulsion of perfluoropolyoxyalkylenes previously prepared, in such an amount to obtain 2 g of fluorinated surfactant per H20 liter; 0.26 g per H20 liter of isopropanol. The autoclave was then brought to the reaction temperature of 75C, charged with 1 absolute bar of CH4 and then with TFE to a working pressure of 20 absolute bar. When the working pressure was reached, 300 ml of a 0.00123 molar aqueous solution of potassium persulphate (KPS) were fed.
The working pressure was maintained constant during the reaction by feeding TFE.
After 140 minutes the reaction was stopped by cooling the autoclave at room temperature. The emulsion was then discharged and the polymer coagulated by mechanical stirring, separated from the aqueous medium and then washed with H20 and dried. 40 g of TFE/PPVE copolymer (about 98/2 by mols) have been obtained. The measured values of Melt Flow Index ~MFI) and productivity ~Rp) are reported in Table 1.
The productivity is expressed as polymer g/lH20/min.
EXA~P~E 2 ~comparative) The same procedure of Example 1 was followed, with the sole difference that isopropanol was not added. After 140 minutes, 1560 g of TFE/PPVE copolymer were obtained. The data are reported in Table 1.
EXAMPL~ 3 ~comparative) Example 2 was repeated, with the sole difference that methane was introduced with a pressure of 6.5 absolute bar.
After 140 minutes, 490 g of TFE/PPVE copolymer were 11 21t ~
obtained. The data are reported in Table 1.
EXAMPLE 4 (comparative) The same procedure of Example 1 was followed, with the sole difference that methane was not introduced. After 140 minutes, 600 g of TFE/PPVE copolymer were obtained. The data are reported in Table 1.
EXAMæLE 5 Example 1 was repeated following the same procedure, with the sole difference that, instead of isopropanol, pinacol was employed, in an amount of 0.33 g per H2O liter.
After 140 minutes, 560 g of TFE/PPVE copolymer were obtained. The data are reported in Table 1.
ExAMæLE 6 (comparative) The same procedure of Example 5 was followed, with the sole difference that methane was not introduced. After 140 minutes, 1100 g of TFE/PPVE copolymer have been obtained.
The data are reported in Table 1.
~A~PL~ 7 Example 1 was repeated following the same procedure, with the sole difference that, instead of isopropanol, ter-butanol was utilized, in an amount of 0.52 g per H2O liter.
After 140 minutes, 400 g of TFE/PPVE copolymer were ob-tained. The data are reported in Table 1.
E~A~PLE 8 (comparative) The same procedure of Example 7 was followed, with the sole difference that methane was not introduced. After 140 minutes, 950 g of TFE/PPVE copolymer were obtained. The data are reported in Table 1.
OS ~ p~ ~,. r., 2119~
ExA~æLE 9 -~
An AISI 316 chromium steel 5 l autoclave, equipped with a stirrer working at 570 rpm, was evacuated and there were introduced in sequence: 3.4 l of demineralized water; the perfluoropolyoxyalkylene microemulsion previously prepared, in such an amount to obtain 18 g of fluorinated surfactant;
64 g of terbutanol; 3 g of n-pentane. The autoclave was then brought to the reaction temperature of 75C and charged with ethylene and TFE in such an amount to obtain, at the working pressure of 22 absolute bar, an ethylene/TFE ratio in the gaseous phase equal to about 20/80 by mols. When the working ;
pressure was reached, 1.5 g of KPS dissolved in 100 ml of water were fed. The working pressure was maintained constant during the reaction by feeding an ethylene/TFE mixture in molar ratio 49/51. -After 151 minutes the reaction was stopped by cooling the autoclave at room temperature. The emulsion was then discharged and the polymer coagulated (by addition of HCl at 37% under mechanical stirring), separated from the aqueous medium and then washed with H2O and dried. 650 g of ~ ;
ethylene/TFE copolymer (about 48/52 in mols) were obtained.
The measured values of Melt Flow Index (MFI) and ;
productivity (Rp) are reported in Table 2.
A~PL~ 10 (comparative) The same procedure of Example 9 was followed, with the . ~
sole difference that terbutanol was not added. After 118 minutes, 650 g of ethylene/TFE copolymer were obtained. The ~-data are reported in Table 2. ~
,,"." ''';~
2 1 ~ 9 ~
EXAMPLE 11 (comparative) -~
The same procedure of Example 9 was followed, with the sole difference that n-pentane was not added. After 90 minutes, 650 g of ethylene/TFE copolymer were obtained. The data are reported in Table 2.
' ~`'',`
;. ', `
~;'"'''~''' 14 21~9~
: ' EX. CH4 ALCOHOLMFI (g/10') Rp (bar) (g/lH20)(ASTM D3307-86) ~g/lH20/min) _ isopropanol 1 1 0.26 > 100 0.086 2 1 __ 0.6 3.4 3 6.5 _ 24.2 1 4 __ 0.26 s.f. 1.3 pinacol 1 0.33 3.2 1.21 6 __ 0.33 s.f. 2.7 . . ..
terbutanol 7 1 0.52 20 0.87 ~ __ 0.52 s.f. 2.06 s.f, = scarce fluidity: MFI not measurable.
.~
..... : :
FX. n-CsHl2 ALCOHOLMFI ~g/10~) Rp l ¦_ (g) (g) (ASTM D3159-83) (g/lH20/min) ¦
terbutanol I -9 3 64 56.3 1.22 3 __ s.f. 1.56 11 __ 64 s.f. 2.05 s.f. = scarce fluidity: MFI not measurable. -~
: ...-~
' : ~.
:.~: ::
Moreover, the addition of the branched chain alcohol makes effective as chain transfer agents also those hydrocarbons which have low activity by themselves. For ;~
instance, with the process object of the present invention it is possible to employ as chain transfer agents n-pentane and other hydrocarbons liquid at room temperature, which can be more easily handled and dosed if compared with gaseous hydrocarbons such as methane and ethane.
Examples of hydrogenated chain transfer agents employable in the process object of the present invention are: methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane, l,l-difluoroethane, or mixtures thereof. -~
~ xamples of branched chain aliphatic alcohols employable in the process object of the present invention are: isopropanol, terbutanol, pinacol, 2,4-dimethyl-3-pentanol, 2,4,4-trimethyl-1,3-pentandiol, or mixtures thereof.
The amount of hydrogenated chain transfer agent and of ' ' 21~ 9 L~ 1 1 aliphatic alcohol to be used can vary within a very wide range and depends on various factors, such as the polymerization conditions (in particular temperature, presence of co-solvents, etc.), the monomer nature, besides, of course, on the structure of the chain transfer agent and of the alcohol. According to the characteristics of the final product to be obtained, the skilled person will be able to choose case by case the most suitable concentrations of chain transfer agent and of alcohol. For indicative purposes the weight ratio between alcohol and transfer agent can vary from 0.005 to 500, preferably from 0.05 to 50.
The (co)polymerization is carried out in aqueous emulsion according to methods well known in the art (see for instance US patents 3,635,926 and 4,426,501). Preferably, the process is carried out in aqueous emulsion in the presence of an emulsion or microemulsion of perfluoropoly~
oxyalkylenes, according to what described in US Patents 4,789,717 and 4,864,006. ~;~
As known in the art, the (co)polymerization reaction occurs in the preæence of suitable initiators, such as inorganic (for instance, ammonium or alkali metal per-sulphates) or organic (for instance, disuccinylperoxide, terbutyl-hydroperoxide, diterbutyl-peroxide) peroxides, or also azo-compounds (see US 2,515,628 and 2,520,338). It is also possible to employ organic or inorganic redox systems, such as ammonium persulphate/sodium sulphite, hydrogen peroxide/aminoiminomethansulphinic acid. The amount of ",.~" ,,,., . ~ . ~, ",,," ,,,,,, 1 ,.
2~9~
radical initiator is that commonly employed for the (co)polymerization of fluorinated olefinic monomers, and it is generally comprised between 0.003% and 2% by weight with respect to the total amount of (co)polymerized monomers.
As known, the emulsion technique requires also the presence of surfactants. Among the various kinds of surfactants employable in the process object of the present invention, we would like to cite in particular the products of formula:
R~-X- M~
where Rf is a (per)fluoroalkyl chain Cs-C16 or a (per)fluoro-polyoxyalkylene chain, X~ is -COO~ or -S03-, M~ is selected from H~, NH~, alkali metal ion. The most commonly used are:
ammonium perfluoro-octanoate, (per)fluoropolyoxyalkylenes end-capped with one or more carboxylic groups, etc.
The reaction temperature can vary within wide ranges, generally comprised between 10 and 150C, preferably be~ween 50 and 80C, while the pressure is generally comprised between 10 and 100 bar, preferably between 15 and 40 bar.
The process object of the present invention can be employed with all kinds of fluorinated olefinic monomers, optionally containing hydrogen and/or chlorine and/or bromine and/or iodine and/or oxygen, provided that they are able to give rise to (co)polymers for reaction with radical initiators in aqueous emulsion. Among them we cite:
perfluoroolefins C2-C8, such as tetrafluoroethylene (TFE), hexafluoropropene (HFP), hexafluoroisobutene; hydrogenated 21~9411 fluoroolefins C2-C~, such as vinyl fluoride (VF), vinylidene fluoride (VDF) and trifluoroethylene; chloro- and/or bromo~
and/or iodo-fluoroolefins C2_CBI such as chlorotrifluoro-ethylene (CTFE) and bromotrifluoroethylene; perfluorovinyl-ethers CF2=CFOX, where X is a perfluoroalkyl Cl-C6, for instance trifluoromethyl or pentafluoropropyl, or a perfluoro-oxyalkyl Cl-Cg having one or more ethereal groups, for example perfluoro-2-propoxy-propyl; perfluorodioxols.
The fluoroolefins can be also copolymerized with non-fluorinated olefins C2-C8, such as ethylene, propylene, iso-butylene.
Among the copolymers to which the process object of the present invention can be applied are comprised in particular~
(a) "modified'l polytetrafluoroethylene, containing small amounts, generally comprised between 0.1 to 3% by mols, preferably lower than 0.5% by mols, of one or more comonomers such as, for example: perfluoropropene, perfluoroalkylvinylethers, vinylidene fluoride, hexafluoroisobutene, chlorotrifluoroethylenei (b) TFE thermoplastic polymers containing from 0.5 to 8% by mols of at least a perfluoroalkylvinylether, where the alkyl has from 1 to 6 carbon atoms, such as, for instance, TFE/perfluoropropylvinylether and TFE/
perfluoromethylvinylether copolymers;
(c) TFE thermoplastic polymers containing fr~m 2 to 20~ by mols of a perfluoroolefin C3_C~, such as, for example, FEP (TFE/HFP copolymer), to which other comonomers 21~9~11 having vinylether structure can be added in small amounts (lower than 5% by mols) (see for instance US
patent 4,675,380);
(d) TFE or CTFE copolymers with ethylene, propylene or isobutylene, optionally containing a third fluorinated comonomer in amounts comprised between 0.1 and 10% by mols (see for instance US patents 3,624,250 and 4,513,129);
(e) TFE elastomeric copolymers with a perfluoro(oxy)alkyl-vinylether, optionally containing propylene or ethylene, besides lower amounts of a ~'cure-site"
monomer (see for instance US patents 3,467,635 and 4,694,045);
(f) polymers having dielectric characteristics, comprising 60-79% by mols of VDF, 18-22% by mols of trifluoro-ethylene and 3-22% by mols of CTFE (see US patent 5,087,679).
(g) VDF elastomeric polymers, such as VDF/HFP copolymers and VDF/HFP/TFE terpolymers (see, for instance, GB
Patent 888,765 and Kirk-Othmer, "Encyclopedia of Chemical Technology", Vol. 8, pag. 500-515 - 1979);
such polymers can also contain: hydrogenated olefins, such as ethylene and propylene (as described for instance in EP-518,073); perfluoroalkylvinylethersi bromine "cure-site" comonomers and/or terminal iodine atoms, according to what described, for instance, in US-4,243,770, US-4,973,633 and EP-407,937.
(h) polyvinylidenfluoride or "modified~ polyvinyliden-~' ',~' 2 1 ~
fluoride containing little amounts, generally comprisedbetween 0.1 and 10~ by mols, of one or more fluorinated comonomers, such as hexafluoropropene, tetrafluoro-ethylene, trifluoroethylene.
The polymers of the above indicated classes, and in particular the TFE polymers, can be modified with : ~ .
perfluorinated dioxols, according to what described for instance in US-3,865,845, US-3,978,030, EP-73,087, EP~
76,581, EP-80,187.
Some examples are reported hereinbelow, for merely illustrative and not limitative purposes of the invention itself.
Preparation of the perfluoropolyoxyalkylene microemulsion In a glass flask equipped with a stirrer, 29.3 g of a compound of formula:
CF30 - ( CF2 - CF ( CF3 ) O ) n ( CF20 ) ,- CF2COOH
having n/m=10 and average molecular weight of 590, were mixed with 16.3 g of NH~OH at 30~ by volume. 32.6 g of demineralized water and 17.6 g of Galden~R~ D02 of formula:
CF30- (CF2-CF (CF3) O) n (CF20) ,-CF3 having n/m=20 and average molecular weight of 450, were then added. At a temperature of from 60 to 90C the mixture was ;
in the form of a microemulsion and appeared as a limpid, thermodynamically stable solution.
~A~PLE 1 An AISI 316 chromium steel 5 1 autoclave, equipped with a stirrer working at 650 rpm, was evacuated and there were introduced in sequence: 3 1 of demineralized water; 32.33 g .
'.~.
~'' lo 21~
per H2O liter of perfluoropropylvinylether (PPVE); the microemulsion of perfluoropolyoxyalkylenes previously prepared, in such an amount to obtain 2 g of fluorinated surfactant per H20 liter; 0.26 g per H20 liter of isopropanol. The autoclave was then brought to the reaction temperature of 75C, charged with 1 absolute bar of CH4 and then with TFE to a working pressure of 20 absolute bar. When the working pressure was reached, 300 ml of a 0.00123 molar aqueous solution of potassium persulphate (KPS) were fed.
The working pressure was maintained constant during the reaction by feeding TFE.
After 140 minutes the reaction was stopped by cooling the autoclave at room temperature. The emulsion was then discharged and the polymer coagulated by mechanical stirring, separated from the aqueous medium and then washed with H20 and dried. 40 g of TFE/PPVE copolymer (about 98/2 by mols) have been obtained. The measured values of Melt Flow Index ~MFI) and productivity ~Rp) are reported in Table 1.
The productivity is expressed as polymer g/lH20/min.
EXA~P~E 2 ~comparative) The same procedure of Example 1 was followed, with the sole difference that isopropanol was not added. After 140 minutes, 1560 g of TFE/PPVE copolymer were obtained. The data are reported in Table 1.
EXAMPL~ 3 ~comparative) Example 2 was repeated, with the sole difference that methane was introduced with a pressure of 6.5 absolute bar.
After 140 minutes, 490 g of TFE/PPVE copolymer were 11 21t ~
obtained. The data are reported in Table 1.
EXAMPLE 4 (comparative) The same procedure of Example 1 was followed, with the sole difference that methane was not introduced. After 140 minutes, 600 g of TFE/PPVE copolymer were obtained. The data are reported in Table 1.
EXAMæLE 5 Example 1 was repeated following the same procedure, with the sole difference that, instead of isopropanol, pinacol was employed, in an amount of 0.33 g per H2O liter.
After 140 minutes, 560 g of TFE/PPVE copolymer were obtained. The data are reported in Table 1.
ExAMæLE 6 (comparative) The same procedure of Example 5 was followed, with the sole difference that methane was not introduced. After 140 minutes, 1100 g of TFE/PPVE copolymer have been obtained.
The data are reported in Table 1.
~A~PL~ 7 Example 1 was repeated following the same procedure, with the sole difference that, instead of isopropanol, ter-butanol was utilized, in an amount of 0.52 g per H2O liter.
After 140 minutes, 400 g of TFE/PPVE copolymer were ob-tained. The data are reported in Table 1.
E~A~PLE 8 (comparative) The same procedure of Example 7 was followed, with the sole difference that methane was not introduced. After 140 minutes, 950 g of TFE/PPVE copolymer were obtained. The data are reported in Table 1.
OS ~ p~ ~,. r., 2119~
ExA~æLE 9 -~
An AISI 316 chromium steel 5 l autoclave, equipped with a stirrer working at 570 rpm, was evacuated and there were introduced in sequence: 3.4 l of demineralized water; the perfluoropolyoxyalkylene microemulsion previously prepared, in such an amount to obtain 18 g of fluorinated surfactant;
64 g of terbutanol; 3 g of n-pentane. The autoclave was then brought to the reaction temperature of 75C and charged with ethylene and TFE in such an amount to obtain, at the working pressure of 22 absolute bar, an ethylene/TFE ratio in the gaseous phase equal to about 20/80 by mols. When the working ;
pressure was reached, 1.5 g of KPS dissolved in 100 ml of water were fed. The working pressure was maintained constant during the reaction by feeding an ethylene/TFE mixture in molar ratio 49/51. -After 151 minutes the reaction was stopped by cooling the autoclave at room temperature. The emulsion was then discharged and the polymer coagulated (by addition of HCl at 37% under mechanical stirring), separated from the aqueous medium and then washed with H2O and dried. 650 g of ~ ;
ethylene/TFE copolymer (about 48/52 in mols) were obtained.
The measured values of Melt Flow Index (MFI) and ;
productivity (Rp) are reported in Table 2.
A~PL~ 10 (comparative) The same procedure of Example 9 was followed, with the . ~
sole difference that terbutanol was not added. After 118 minutes, 650 g of ethylene/TFE copolymer were obtained. The ~-data are reported in Table 2. ~
,,"." ''';~
2 1 ~ 9 ~
EXAMPLE 11 (comparative) -~
The same procedure of Example 9 was followed, with the sole difference that n-pentane was not added. After 90 minutes, 650 g of ethylene/TFE copolymer were obtained. The data are reported in Table 2.
' ~`'',`
;. ', `
~;'"'''~''' 14 21~9~
: ' EX. CH4 ALCOHOLMFI (g/10') Rp (bar) (g/lH20)(ASTM D3307-86) ~g/lH20/min) _ isopropanol 1 1 0.26 > 100 0.086 2 1 __ 0.6 3.4 3 6.5 _ 24.2 1 4 __ 0.26 s.f. 1.3 pinacol 1 0.33 3.2 1.21 6 __ 0.33 s.f. 2.7 . . ..
terbutanol 7 1 0.52 20 0.87 ~ __ 0.52 s.f. 2.06 s.f, = scarce fluidity: MFI not measurable.
.~
..... : :
FX. n-CsHl2 ALCOHOLMFI ~g/10~) Rp l ¦_ (g) (g) (ASTM D3159-83) (g/lH20/min) ¦
terbutanol I -9 3 64 56.3 1.22 3 __ s.f. 1.56 11 __ 64 s.f. 2.05 s.f. = scarce fluidity: MFI not measurable. -~
: ...-~
' : ~.
:.~: ::
Claims (10)
1. A radical (co)polymerization process of one or more fluorinated olefinic monomers, optionally in association with one or more non-fluorinated olefins, wherein said monomers are (co)polymerized in aqueous emulsion, in the presence of a hydrogenated chain transfer agent selected from hydrogen, aliphatic hydrocarbons and fluorohydrocarbons having from 1 to 20 carbon atoms, and of a branched chain aliphatic alcohol having from 3 to 14 carbon atoms and characterized by a ratio among the number of hydroxyl groups and the number of methyl groups lower than or equal to 0.5.
2. The process according to claim 1, wherein said monomers are (co)polymerized in aqueous emulsion in the presence of an emulsion or microemulsion of perfluoropolyoxy-alkylenes.
3. The process according to claim 1 or 2, wherein the hydrogenated chain transfer agent is an aliphatic hydrocarbon or fluorohydrocarbon having from 1 to 8 carbon atoms.
4. The process according to claim 3, wherein the hydrogenated chain transfer agent is selected from:
methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane, 1,1-difluoroethane, or mixtures thereof.
methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane, 1,1-difluoroethane, or mixtures thereof.
5. The process according to anyone of the preceding claims, wherein the branched chain aliphatic alcohol has from 3 to 8 carbon atoms.
6. The process according to claim 5, wherein the branched chain aliphatic alcohol is selected from: isopropanol, terbutanol, pinacol, 2,4-dimethyl-3-pentanol, 2,4,4-trimethyl-1,3-pentandiol, or mixtures thereof.
7. The process according to anyone of the preceding claims, wherein the weight ratio between alcohol and chain transfer agent is comprised between 0.005 and 500.
8. The process according to claim 7, wherein the weight ratio between alcohol and chain transfer agent is comprised between 0.05 and 50.
9. The process according to anyone of the preceding claims, in which the fluorinated olefinic monomers are selected from: perfluoroolefins C2-C8; hydrogenated fluoroolefins C2-C8; chloro- and/or bromo- and/or iodo-fluoroolefins C2-C8; perfluorovinylethers CF2=CFOX, where X is a perfluoroalkyl C1-C6 or a perfluoro-oxyalkyl C1-C9 having one or more ethereal groups;
perfluorodioxols.
perfluorodioxols.
10. The process according to anyone of the preceding claims, wherein the non-fluorinated olefins have from 2 to 8 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI93A000551 | 1993-03-23 | ||
| ITMI930551A IT1271136B (en) | 1993-03-23 | 1993-03-23 | PROCESS OF (CO) POLYMERIZATION IN AQUEOUS EMULSION OF FLUORINATED OLEFINIC MONOMERS |
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| Publication Number | Publication Date |
|---|---|
| CA2119411A1 true CA2119411A1 (en) | 1994-09-24 |
Family
ID=11365454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002119411A Abandoned CA2119411A1 (en) | 1993-03-23 | 1994-03-18 | (co) polymerization process in aqueous emulsion of fluorinated olefinic monomers |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5516863A (en) |
| EP (1) | EP0617058B1 (en) |
| JP (1) | JP3383064B2 (en) |
| KR (1) | KR100296906B1 (en) |
| AT (1) | ATE158310T1 (en) |
| CA (1) | CA2119411A1 (en) |
| DE (1) | DE69405618T2 (en) |
| ES (1) | ES2108313T3 (en) |
| IT (1) | IT1271136B (en) |
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| US5590654A (en) | 1993-06-07 | 1997-01-07 | Prince; Martin R. | Method and apparatus for magnetic resonance imaging of arteries using a magnetic resonance contrast agent |
| IT1266647B1 (en) * | 1993-10-29 | 1997-01-09 | Ausimont Spa | PROCESS OF (CO) POLYMERIZATION OF FLUORINATED OLEPHINE MONOMERS IN AQUEOUS EMULSION |
| IT1271621B (en) * | 1994-03-21 | 1997-06-04 | Ausimont Spa | PROCESS FOR THE PREPARATION OF THERMOPLASTIC FLUOROPOLYMERS CONTAINING HYDROGEN |
| IT1274711B (en) | 1994-08-04 | 1997-07-24 | Ausimont Spa | PROCESS FOR THE PREPARATION OF FLUOROPOLYMERS CONTAINING HYDROGEN THROUGH (CO) SUSPENSION POLYMERIZATION |
| IT1270703B (en) * | 1994-11-17 | 1997-05-07 | Ausimont Spa | MICROEMULSIONS OF FLUOROPOLYXIALKYLENES IN A MIXTURE WITH HYDROCARBONS, AND THEIR USE IN PROCESSES OF (CO) POLYMERIZATION OF FLUORINATED MONOMERS |
| WO2000032655A1 (en) * | 1998-11-30 | 2000-06-08 | E.I. Du Pont De Nemours And Company | Fluoromonomer polymerization |
| FR2804438A1 (en) * | 2000-01-31 | 2001-08-03 | Atofina | Preparation of reduced-yellowing fluorinated polymer is carried out by aqueous emulsion polymerisation of vinylidene fluoride (and other monomers) using a lithium perfluoroalkanoate as surfactant |
| IT1317847B1 (en) * | 2000-02-22 | 2003-07-15 | Ausimont Spa | PROCESS FOR THE PREPARATION OF WATER DISPERSIONS OF FLUOROPOLYMERS. |
| IT1318596B1 (en) * | 2000-06-23 | 2003-08-27 | Ausimont Spa | THERMOPROCESSABLE TFE COPOLYMERS. |
| IT1318594B1 (en) * | 2000-06-23 | 2003-08-27 | Ausimont Spa | POLYMERIZATION PROCESS OF SULPHONIC MONOMERS. |
| US6649720B2 (en) | 2001-02-14 | 2003-11-18 | Atofina Chemicals, Inc. | Ethane as a chain transfer agent for vinylidene fluoride polymerization |
| DE60121291T2 (en) * | 2001-03-26 | 2008-01-03 | 3M Innovative Properties Co., Saint Paul | Improved process for the polymerization of fluorine-containing monomers in aqueous emulsion |
| US7125941B2 (en) | 2001-03-26 | 2006-10-24 | 3M Innovative Properties Company | Aqueous emulsion polymerization process for producing fluoropolymers |
| US6734264B1 (en) * | 2002-12-16 | 2004-05-11 | Atofina Chemicals, Inc. | Chain transfer agent |
| FR2850387B1 (en) * | 2003-01-23 | 2005-03-04 | Atofina | PROCESS FOR PRODUCING PVDF |
| ATE529451T1 (en) | 2003-11-17 | 2011-11-15 | 3M Innovative Properties Co | AQUEOUS PTFE DISPERSIONS WITH A LOW CONTENT OF FLUORINATED EMULSIFIERS |
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| CA2855742C (en) | 2011-11-24 | 2019-10-29 | Cfs Concrete Forming Systems Inc. | Stay-in place formwork with engaging and abutting connections |
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| US10151119B2 (en) | 2012-01-05 | 2018-12-11 | Cfs Concrete Forming Systems Inc. | Tool for making panel-to-panel connections for stay-in-place liners used to repair structures and methods for using same |
| US9453345B2 (en) | 2012-01-05 | 2016-09-27 | Cfs Concrete Forming Systems Inc. | Panel-to-panel connections for stay-in-place liners used to repair structures |
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| CA2932453C (en) | 2013-12-06 | 2022-07-12 | Cfs Concrete Forming Systems Inc. | Structure cladding trim components and methods for fabrication and use of same |
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| EP3607152B1 (en) | 2017-04-03 | 2023-09-27 | CFS Concrete Forming Systems Inc. | Longspan stay-in-place ceiling liners |
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| US2968649A (en) * | 1958-12-04 | 1961-01-17 | Du Pont | Elastomeric terpolymers |
| US3467635A (en) * | 1964-10-30 | 1969-09-16 | Du Pont | Copolymers of tetrafluoroethylene and olefins curable to elastomers |
| US3635926A (en) * | 1969-10-27 | 1972-01-18 | Du Pont | Aqueous process for making improved tetrafluoroethylene / fluoroalkyl perfluorovinyl ether copolymers |
| US3624250A (en) * | 1970-01-20 | 1971-11-30 | Du Pont | Copolymers of ethylene/tetrafluoroethylene and of ethylene/chlorotrifluoroethylene |
| US3865845A (en) * | 1971-02-24 | 1975-02-11 | Paul Raphael Resnick | Fluorinated dioxoles |
| US3978030A (en) * | 1973-08-01 | 1976-08-31 | E. I. Du Pont De Nemours And Company | Polymers of fluorinated dioxoles |
| JPS53125491A (en) * | 1977-04-08 | 1978-11-01 | Daikin Ind Ltd | Fluorine-containing polymer easily curable and its curable composition |
| JPS5645911A (en) * | 1979-09-25 | 1981-04-25 | Asahi Glass Co Ltd | Production of ion-exchangeable fluorinated polymer |
| JPS5838707A (en) * | 1981-08-20 | 1983-03-07 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Amorphous copolymer of perfluoro-2,2-dimethyl- 1,3-dioxol |
| US4360652A (en) * | 1981-08-31 | 1982-11-23 | Pennwalt Corporation | Method of preparing high quality vinylidene fluoride polymer in aqueous emulsion |
| US4429143A (en) * | 1981-09-28 | 1984-01-31 | E. I. Du Pont De Nemours & Co. | Cyclic monomers derived from trifluoropyruvate esters |
| US4399264A (en) * | 1981-11-19 | 1983-08-16 | E. I. Du Pont De Nemours & Co. | Perfluorodioxole and its polymers |
| US4426501A (en) * | 1983-01-17 | 1984-01-17 | E. I. Du Pont De Nemours And Company | Emulsion copolymerization process using comonomer solubility affecting additives |
| JPS59197411A (en) * | 1983-04-25 | 1984-11-09 | Daikin Ind Ltd | Ethylene/tetrafluoroethylene (or chlorotrifluoroethylene) copolymer |
| US4694045A (en) * | 1985-12-11 | 1987-09-15 | E. I. Du Pont De Nemours And Company | Base resistant fluoroelastomers |
| US4675380A (en) * | 1985-10-25 | 1987-06-23 | E. I. Du Pont De Nemours And Company | Melt-processible tetrafluoroethylene/perfluoroolefin copolymer granules and processes for preparing them |
| IT1189092B (en) * | 1986-04-29 | 1988-01-28 | Ausimont Spa | POLYMERIZATION PROCESS IN WATER DISPERSION OF FLUORINATED MONOMERS |
| JPS62285907A (en) * | 1986-06-03 | 1987-12-11 | Asahi Glass Co Ltd | Production of tetrafluoroethylene/fluorovinyl ether copolymer |
| IT1204903B (en) * | 1986-06-26 | 1989-03-10 | Ausimont Spa | POLYMERIZATION PROCESS IN WATER DISPERSION OF FLORATED MONOMERS |
| IT1230650B (en) * | 1988-11-17 | 1991-10-28 | Ausimont Srl | PROCEDURE FOR THE PREPARATION OF TETRAFLUOROETHYLENE ETHYLENE COPOLYMERS |
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| IT1235545B (en) * | 1989-07-10 | 1992-09-09 | Ausimont Srl | FLUOROELASTOMERS EQUIPPED WITH BETTER PROCESSABILITY AND PREPARATION PROCEDURE |
| IT1247934B (en) * | 1991-05-15 | 1995-01-05 | Ausimont Spa | VINYLIDENFLUORIDE-BASED FLUOROELASTOMERS, EQUIPPED WITH SUPERIOR BASIC RESISTANCE |
-
1993
- 1993-03-23 IT ITMI930551A patent/IT1271136B/en active IP Right Grant
-
1994
- 1994-03-04 DE DE69405618T patent/DE69405618T2/en not_active Expired - Fee Related
- 1994-03-04 EP EP94103287A patent/EP0617058B1/en not_active Expired - Lifetime
- 1994-03-04 ES ES94103287T patent/ES2108313T3/en not_active Expired - Lifetime
- 1994-03-04 AT AT94103287T patent/ATE158310T1/en not_active IP Right Cessation
- 1994-03-18 CA CA002119411A patent/CA2119411A1/en not_active Abandoned
- 1994-03-22 KR KR1019940005722A patent/KR100296906B1/en not_active IP Right Cessation
- 1994-03-23 JP JP07643494A patent/JP3383064B2/en not_active Expired - Fee Related
-
1995
- 1995-08-18 US US08/516,685 patent/US5516863A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR940021592A (en) | 1994-10-19 |
| US5516863A (en) | 1996-05-14 |
| IT1271136B (en) | 1997-05-27 |
| JPH0790008A (en) | 1995-04-04 |
| JP3383064B2 (en) | 2003-03-04 |
| DE69405618T2 (en) | 1998-04-23 |
| EP0617058A1 (en) | 1994-09-28 |
| ITMI930551A1 (en) | 1994-09-23 |
| DE69405618D1 (en) | 1997-10-23 |
| ES2108313T3 (en) | 1997-12-16 |
| ITMI930551A0 (en) | 1993-03-23 |
| ATE158310T1 (en) | 1997-10-15 |
| KR100296906B1 (en) | 2001-10-24 |
| EP0617058B1 (en) | 1997-09-17 |
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